1、Designation: C1379 10Standard Test Method forAnalysis of Urine for Uranium-235 and Uranium-238Isotopes by Inductively Coupled Plasma-MassSpectrometry1This standard is issued under the fixed designation C1379; the number immediately following the designation indicates the year oforiginal adoption or,
2、 in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of the con-centration of uranium-235 a
3、nd uranium-238 in urine usingInductively Coupled Plasma-Mass Spectrometry. This testmethod can be used to support uranium facility bioassayprograms.1.2 This method detection limits for235U and238U are 6ng/L. To meet the requirements ofANSI N13.30, the minimumdetectable activity (MDA) of each radionu
4、clide measured mustbe at least 0.1 pCi/L (0.0037 Bq/L). The MDA translates to 47ng/L for235U and 300 ng/L for238U. Uranium 234 cannot bedetermined at the MDAwith this test method because of its lowmass concentration level equivalent to 0.1 pCi/L.1.3 The digestion and anion separation of urine may no
5、t benecessary when uranium concentrations of more than 100 ng/Lare present.1.4 UnitsThe values stated in picoCurie per liter units areto be regarded as standard. The values given in parentheses aremathematical conversions to SI units that are provided forinformation only and are not considered stand
6、ard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.NOTE 1Warni
7、ng: The ICP-MS is a source of intense ultravioletradiation from the radio frequency induced plasma. Protection from radiofrequency radiation and UV radiation is provided by the instrument undernormal operation.2. Referenced Documents2.1 ASTM Standards:2C859 Terminology Relating to Nuclear MaterialsC
8、1310 Test Method for Determining Radionuclides in Soilsby Inductively Coupled Plasma-Mass Spectrometry UsingFlow Injection Preconcentration (Withdrawn 2011)3C1345 Test Method for Analysis of Total and IsotopicUranium and Total Thorium in Soils by InductivelyCoupled Plasma-Mass SpectrometryD1193 Spec
9、ification for Reagent Water2.2 Other Documents:ANSI N13.30 Radiological Measurement QualityDOE Order 5480.11 Radiological Measurements Quality3. Terminology3.1 For terms in this document, see Terminology C859.3.2 Definitions:3.2.1 isobar, nany atom that has the same atomic massnumber as another atom
10、 but a different atomic number.3.3 Acronyms:3.3.1 AMU, natomic mass unit3.3.2 CB, ncalibration blank3.3.3 COC, nchain of custody3.3.4 CVS, ncalibration verification standard3.3.5 ICS, ninstrument check standard3.3.6 IDL, ninstrument detection limit3.3.7 LCS, nlaboratory control sample3.3.8 MDA, nmin
11、imum detectable activity1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved Jan. 1, 2010. Published February 2010. Originallyapproved in 1997. Last previous edition a
12、pproved in 2004 as C1379 04. DOI:10.1520/C1379-10.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandardsvolume information, refer to the standards Document Summary page onthe ASTM website3The last app
13、roved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesNOTICE: This standard has either been superseded and replaced by a new version or withdrawn.Contact ASTM Internation
14、al (www.astm.org) for the latest information13.3.9 m/e, nmass/charge ratio3.3.10 RMDA, nrequired minimum detectable activity3.3.11 % RDS, npercent relative standard deviation(1Standard Deviation / Mean) * 1004. Summary of Test Method4.1 A urine sample is digested and wet oxidized withconcentrated ni
15、tric and hydrochloric acids to solubilize ura-nium and to destroy the organic matter. Uranium is selectivelyseparated from the chloride salts by an anion exchange resinand is eluted with dilute nitric acid. The235U and238U isotopesare determined by ICP-MS.5. Significance and Use5.1 DOE Order 5480.11
16、 and ANSI N13.30 require thatinternal dose assessments be made as part of the bioassayprogram for nuclear facility workers. For indirect bioassay ofuranium workers, the uranium isotopes must be measuredalong with the total uranium in urine samples. The RMDA foreach uranium isotope is 0.1 pCi/L.5.2 T
17、his method is applicable for measuring235U and238Uat the RMDA. Because of extremely low mass concentration(because of the high specific activity),234U cannot be mea-sured without additional sample preconcentration.NOTE 2Column chromatography separations and concentration of234U using manual or flow-
18、injection preconcentration followed byICP-MS isotopic determination are described in Test Methods C1310 andC1345. These methods focus on environmental soil sample analysis, butwith some development, may be applicable to digested urine samples. The234U concentration can be calculated based on an enri
19、chment gradient forworkers in uranium enrichment plants, and internal dose assessments canbe made.NOTE 3Use of high resolution ICP-MS may also be used to obtainlower detection limits.46. Interferences6.1 No known isobaric elemental interferences occur fordetermining235U and238U using this test metho
20、d.NOTE 4Bismuth, such as found in some antacids, may interfere withthe analysis by using binding sites on the resin or biasing the internalstandard measurement on the ICP-MS analysis.7. Apparatus7.1 Inductively Coupled Plasma-Mass Spectrometer,computer-controlled, multi-channel peristaltic pump, and
21、 anautosampler.5-77.2 Appropriate sized disposable graduated test tube withcap that will accommodate the autosampler.7.3 Twelve-mL disposable polyethylene column or suitablesize with frit.7.4 Vacuum manifold chamber with regulator valve,vacuum gage, vacuum relief valve, and a vacuum manifoldbeaker r
22、ack (optional).8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications
23、are available.8Other grades of reagentsmay be used, provided it is first ascertained that the reagent isof sufficiently high purity to permit its use without lesseningthe accuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reage
24、nt water, as ASTM,Type I water as defined in Specification D1193.8.3 Nitric Acid (sp gr 1.42)concentrated nitric acid(HNO3).8.4 Hydrochloric Acid (sp gr 1.18)concentrated hydro-chloric acid (HCl).8.5 Nitric Acid (8M)Add 500 mL of concentrated HNO3to 500 mL of water, and mix.8.6 Nitric Acid (0.8 M)Ad
25、d 50 mL of concentrated HNO3to 950 mL of water, and mix.8.7 Nitric Acid (0.01 M)Add 1.25 mLof 8M HNO3to 950mL of water, and dilute to a final volume of 1000 mL, and mix.8.8 Hydrochloric Acid (6 M)Add 500 mL of concentratedHCl to 500 mL of water, and mix.8.9 Argon Gaspurity 99.99 % or better recommen
26、ded.8.10 Standard Metals Stock SolutionsPrepare or purchasecertified traceable stock or equivalent certified solutions ofberyllium, bismuth, cobalt, indium, lanthanum, lead,magnesium, and uranium to be used for the tuning solution,calibration, spiking, mass calibration, and internal standard, oras r
27、ecommended by the manufacturer.8.11 Isotopic Stock SolutionPrepare two uranium isotopicstock solutions each containing 100 000 ng/L of total uraniumpurchased from a nationally recognized standards body such asNBL, NBL CRM U030A (3 %235U) and NBL CRM U150(15 %235U) uranium reference materials, or equ
28、ivalent, arerecommended.4Krystek, P. and Ritsema, R., “Determination of Uranium in Urine Measure-ment of Isotope Ratios and Quantification by Use of Inductively Plasma MassSpectrometry,”Anal. Bioanal. Chem., v. 374:226229, 2002.5Jarvis, K. E., Gray, A. L., and Houk, R. S., Handbook of Inductively Co
29、upledPlasma Mass Spectrometry, Blackie, 1992.6Inductively Coupled Plasma-Mass Spectrometry, Method 6020, USEPA, “SW-846 Test Methods for Evaluating Solid Wastes,” Third Edition, Agency, November1990.Available from US Department of Commerce, National Technical InformationService, Springfield, VA 2216
30、1.7ASTM Special Technical Publication 1291: Applications of InductivelyCoupled Plasma-Mass Spectrometry to Radionuclide Determinations, Morrow, R.W. and Crain, J. S., eds, American Society for Testing Materials, January 1996.8Reagent Chemicals, American Chemical Society Specifications, AmericanChemi
31、cal Society, Washington, D. C. For suggestions on the testing of reagents notlisted by the American Chemical Society, Washington, D. C. For suggestions on thetesting of reagents not listed by the American Chemical Society, see AnalarStandards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U. K.,
32、 and theUnited States Pharmacopeia and National Formulary, U.S. Pharmacopeial Con-vention (USPC), Rockville, MD.C1379 1028.12 Calibration Stock SolutionPrepare a uranium cali-bration stock solution containing 100 000 ng/Lof total uraniumcontaining 50 %235U, such as NBL CRM U500 (50 %235U).8.13 The m
33、ass calibration and stability check of ICP-MSwill require the preparation of a tuning solution that follows theinstrument manufacturers recommended operating conditions.8.13.1 The tuning stock solution can be prepared by addingan aliquot each of stock standard solutions of the elementsrecommended by
34、 the ICP-MS instrument manufacturer towater and 5 parts volume concentrated HNO3per 100 partswater to the recommended concentration.8.13.2 The daily tuning solution should be prepared bydiluting an aliquot of the tuning stock solution (see 8.13.1) and1 part volume concentrate HNO3per 100 parts water
35、. The dailytuning solution concentration for each analyte should be theinstrument manufacturers suggested operating concentration.8.14 Prior to the ICP-MS analysis for total uranium andisotopic concentration, the following QC standards, calibrationstandards, internal standard, and rinse solution are
36、 recom-mended and should be included in the analytical run (seeAppendix X1 for a suggested QC protocol for this practice).8.14.1 Rinse SolutionAdd 1 part concentrated HNO3to100 parts water. Prepare a sufficient quantity to flush theICP-MS and autosampler between calibration standards, QCsamples, and
37、 samples.8.14.2 Uranium Calibration StandardsA minimum offour calibration standards should be prepared containing 50ng/L, 500 ng/L, 1000 ng/L, and 2000 ng/L total uranium bydiluting the uranium calibration stock solution (see 8.12).These calibration standards shall be prepared in 1 part volumeconcen
38、trated HNO3per 100 parts water and contain 50 %235Uand238U isotopic content.8.14.3 Instrument Check Standard (ICS)The ICS shouldbe prepared by diluting a NBL CRM U150 uranium stocksolution (see 8.11) to a total uranium concentration of 100 ng/L(15 ng/L235U and 85 ng/L238U). Prepare this solution in
39、1 partvolume concentrated HNO3per 100 parts water.8.14.4 Calibration Verification Standard (CVS)The CVSshould be prepared by diluting the NBL CRM U030 uraniumstock solution (see 8.11). The CVS is used for initial andcontinuing calibration verification. Prepare the CVS at aconcentration of 400 ng/L t
40、otal uranium (12 ng/L235U and 388ng/L238U). Prepare the verification standard in 1 part volumeconcentrated HNO3per 100 parts water.NOTE 5Improved precision of the diluted standards prepared in8.14.2-8.14.4 may be obtained by preparing an intermediate dilution (;20times) of the stock solutions in 8.1
41、1 and 8.12. Gravimetric preparation ofthese dilutions is recommended.8.14.5 Calibration BlankPrepare the calibration blank in1 part volume concentrated HNO3per 100 parts water.8.14.6 Internal Control SampleAn aliquot of an internalurine control of known concentration to the analyst should beobtained
42、 from a second additional laboratory source. Thelaboratory control sample is treated exactly as a sampleincluding exposure to all labware, equipment, and reagents.The internal control sample is used to check laboratoryanalytical performance against established limits.8.14.7 Laboratory Control Sample
43、 (LCS)Prepare this con-trol by adding an aliquot of the uranium isotopic standards (see8.11) to water to yield an isotopic concentration within thecalibration range. The LCS is treated exactly as a sample,including exposure to all labware, equipment, and reagents.The LCS is used to determine whether
44、 method performance iswithin accepted control limits.8.14.8 Laboratory Reagent Blank (preparation blank)Analiquot of water that is treated exactly as a sample, includingexposure to all labware, equipment, and reagents that are usedwith other samples. The laboratory reagent blank is used todetermine
45、if method analytes or other interferences are presentin the laboratory environment, the reagents, or apparatus.8.14.9 The recommended concentration for the bismuthinternal standard solution is 20 000 ng/Bi/L. The bismuthinternal standard stock solution should be prepared by addingthe required volume
46、 of the bismuth standard stock solution (see8.10) to approximately 100 mL of water. Add 2 parts concen-trated HNO3per 100 parts water, and dilute solution with waterfor the final volume.8.15 Anion exchange resin, 50100 or 100200 mesh (chlo-ride form).99. Sampling, Test Specimens, and Test Units9.1 U
47、rine samples are to be refrigerated at 4C untilanalysis. Preservatives may be used if deemed necessary toensure stability.49.2 All chain of custody requirements described inlaboratory-specific operating procedures must be followed.10. Calibration and Standardization10.1 Follow the instrument manufac
48、turers operatingmanual and laboratory-specific operating procedures for initialstart-up and optimization of the ICP-MS and the associatedcomputer control system and peripheral equipment.10.2 Set up the necessary instrument software files for dataacquisition, calculation, QA and QC data requirements,
49、 archi-val data storage, analytical report preparation, and reportverification, etc.10.3 The instrument, data acquisition, and reporting param-eters shall be determined to meet customer statement of workrequirements.10.4 Introduce the daily tuning solution (see 8.13.2) and setthe mass controls to transmit the first mass m/e 209(Bi) andm/e 238(U), and tune the instrument for optimized response.10.5 Check the mass calibration and resolution with thedaily tuning solution and elements recommended per manu-facturers instrument
